Method for quantifying the pyritic sulfur and the organic sulfur of a rock sample

ABSTRACT

Method for distinctly characterizing and quantifying the pyritic sulfur and the organic sulfur of a sedimentary rock sample. 
     A rock sample is subjected to a heating sequence in an inert atmosphere, the effluents resulting from this heating in an inert atmosphere are continuously oxidized, the SO 2  released is continuously measured, and a pyrolysis sulfur content and a pyrolysis pyritic sulfur content are deduced therefrom. The residue from heating in an inert atmosphere is then heated in an oxidizing atmosphere, the SO 2  released is continuously measured and at least an oxidation sulfur content is deduced therefrom. The pyritic sulfur content is determined from the pyrolysis pyritic sulfur content and from a weighting function taking account of a first parameter representing a pyrite thermal degradation rate, a second parameter representing the impact of the mineral matrix and a third parameter representing the impact of the organic matrix. The organic sulfur content can further be determined from at least the oxidation sulfur content, the pyrolysis sulfur content and the pyritic sulfur content. 
     Application: notably petroleum exploration and exploitation.

FIELD OF THE INVENTION

The present invention relates to the technical field of the petroleum industry, and more particularly to the field of exploration and exploitation of a geological formation wherein hydrocarbons are trapped.

More precisely, the present invention relates to the characterization and quantification of the sulfur present in a sedimentary rock, such as organic matter-rich marine clay.

In order to meet the growing demand for energy, the petroleum industry increasingly turns to the production of unconventional crude oils, which have higher sulfur contents than conventional oils. Now, the sulfur content of an unconventional crude oil and the type of organosulfur compounds it contains are key parameters of the quality of this oil and of the refinery products obtained therefrom. Furthermore, regulations impose increasingly low sulfur contents for refinery products. It is therefore important to be able to precisely characterize and quantify the sulfur present in the rocks these sulfur crude oils originate from.

In the case of petroleum mother rocks, the two main sulfur compounds are organic sulfur and pyritic sulfur. Quantification of the organic sulfur, independently of the pyritic sulfur, is of great importance in petroleum exploration because it allows to exactly know the amount of sulfur associated with the organic matter of mother rocks, which is at the origin of the sulfur present in the oil generated by these mother rocks. In particular, distinct quantification of pyritic sulfur and organic sulfur allows:

to characterize the organic matter type of the mother rock and to predict the quality of the oil generated by the mother rock regarding the sulfur content thereof: indeed, characterization of the organic matter type of mother rocks is conventionally done according to the elemental Carbon (C), Hydrogen (H) and Oxygen (O) content of this organic matter. This conventional characterization of the organic matter type is achieved using the conventional Van Krevelen diagram showing the Hydrogen/Carbon (H/C) atomic ratio as a function of the Oxygen/Carbon (O/C) atomic ratio. The potential of an organic matter to generate oil depending on its H, C and O composition, this diagram allows to distinguish three organic matter types according to the petroleum potential thereof. Indeed, this diagram can be correlated with the origin and the depositional environment of the organic matter. Conventionally, organic matter of lacustrine type (type I), of marine type (type II) and of terrestrial type (type III) is distinguished. Quantification of sulfur in organic matter independently of sulfur in pyrite (or pyritic sulfur) provides an additional parameter enabling finer characterization of the organic matter type, and therefore finer characterization of the depositional environment thereof and of the type of oil it can generate. This finer characterization is performed with the three-dimensional Van Krevelen diagram: H/C as a function of O/C and S^(org)/C, where S^(org) is the organic sulfur content. This extended diagram allows to distinguish more finely the various organic matter types, in particular to identify organic matters of type IS and IIS which have the some origins as types I and II, but containing sulfur, and probably deposited in an anoxic or euxinic environment. This presence of sulfur also indicates that the oil obtained from cracking this organic matter will contain more sulfur. In general, data relative to the organic matter type of the mother rock provide information about the potential of the mother rock to generate oil and about the expected oil quality, notably regarding the sulfur content thereof;

to provide an additional parameter for the oil-mother rock correlation: indeed, the oil-mother rock correlation is a very important survey to be carried out by the person skilled in the art to assess the petroleum system. It consists in making a connection between the oils contained in a reservoir and the mother rock(s) that have generated these oils. Knowing that cracking of the mother rocks containing sulfur-rich organic matter leads to the formation of equally sulfur-rich oils and gas, a method for quantifying the sulfur present in the organic matter, independently of the sulfur in the pyrite, thus provides a key parameter for the oil-mother rock correlation.

BACKGROUND OF THE INVENTION

Patent EP-2,342,557 (U.S. Pat. No. 8,796,035) concerning a device and a method for characterizing and quantifying sulfur in a sedimentary rock or petroleum product sample is notably known. More precisely, the method described in this patent comprises the following steps:

heating the sample considered in a pyrolysis oven in a non-oxidizing atmosphere,

oxidizing part of the pyrolysis effluents and continuously measuring the amount of SO₂ contained in this oxidized effluent part,

transferring the pyrolysis residues to an oxidation oven and continuously measuring the amount of SO₂ contained in the effluents obtained after oxidizing heating of the pyrolysis residue, and

deducing therefrom the sulfur content of the sample.

However, although this method allows to determine the total sulfur content of the sample studied, it does not allow separate quantification of the pyritic sulfur and the organic sulfur. Indeed, this method allows to quantity the total sulfur content of a rock sample via measurement of the sulfur effluents released by this sample during pyrolysis, then oxidation. Two profiles corresponding to sulfur are thus obtained: the first one during the pyrolysis phase and the second during the oxidation phase. As regards the pyrolysis sulfur signal, it is possible to discriminate the organic sulfur from the mineral sulfur due to pyrite as they systematically form two sufficiently distinct peaks. However, in oxidation, the signals of these two sulfur compounds merge, which prevents speciation of the organic and pyritic sulfur. Furthermore, many chemical reactions occur in the rock during analysis. If some involve organic sulfur and/or pyritic sulfur, then they are likely to modify their signals, which adds a difficulty level to the quantification of organic sulfur and pyritic sulfur with the method as described in the aforementioned patent.

The following documents are mentioned in the remainder of the description:

-   Acholla, F. V., Orr, W. L., 1993. Pyrite removal from kerogen     without altering organic matter: The chromous chloride method.     Energy Fuels 7, 406-410. -   Bolin, T. B., 2010. Direct determination of pyrite content in     Argonne premium coals by the use of sulfur X-ray near edge     absorption spectroscopy (S-XANES). Energy and Fuels 24, 5479-5482. -   Canfield, D. E., Raiswell, R., Westrich, J. T., Reaves, C. M.,     Berner, R. A., 1986. The use of chromium reduction in the analysis     of reduced inorganic sulfur in sediments and shales. Chemical     Geology 54, 149-155. -   Orr W., 1986, “Kerogen/asphaltene/sulfur relationships in     sulfur-rich Monterey oils”, Org. Geochem. Vol. 10, pp. 499-516,     1986. -   Vairavamurthy, M. A., Maletic, D., Wang, S., Manowitz, B., Eglinton.     T., Lyons, T., 1997. Characterization of sulfur-containing     functional groups in sedimentary humic substances by X-ray     absorption near-edge structure spectroscopy. Energy and Fuels 11,     546-553. -   Vandenbroucke, M., Largeau, C., 2007. Kerogen origin, evolution and     structure. Organic Geochemistry 38, 719-833.

There are known laboratory methods allowing to distinctly quantify pyritic sulfur and organic sulfur, such as the following techniques:

-   -   Elemental analysis of kerogens, as described in document         (Vandenbroucke and Largeau, 2007). It is one of the commonest         methods routinely used in the laboratory. It is carried out in 2         steps:     -   Kerogen isolation (or organic matter isolation): the kerogen is         isolated from the raw rock through a series of chemical attacks         using hydrochloric and hydrofluoric acid intended to destroy the         mineral matrix, the carbonates and the silicates. Since pyrite         (FeS₂), other metal sulfides and some minor oxides, including         iron oxides, withstand these various chemical attacks, they         remain within the organic residue obtained. Thus, a kerogen         freed from the mineral matrix but still containing pyrite is         obtained:     -   Elemental analysis of iron (by Inductively Coupled Plasma-Atomic         Emission Spectrometry ICP-AES) and sulfur (by infrared         analysis): it is assumed here that the iron present in the         kerogen obtained only comes in form of pyrite (FeS₂). Therefore,         from the measurement of the iron content (ICP-AES) of the         kerogen, the pyrite content can be stoichiometrically         calculated, thus allowing the pyritic sulfur content to be         determined. The organic sulfur content can then be deduced from         the measurement of the sulfur content (IR) of the kerogen, by         difference between the total sulfur (IR measurement) and the         pyritic sulfur.

This first laboratory method according to the prior art involves the following drawbacks:

duration of analysis time: about a week;

it requires preparation and chemical separation steps that are extensive and dangerous since they use strong acids;

it does not enable measurement automation;

it is based on the assumption that all of the iron contained in the organic matter is pyritic. Now, if the iron contained in the organic matter also comes in other forms, such as oxides or sulfides other than FeS₂, the pyritic sulfur content is overestimated and the organic sulfur content is underestimated.

-   -   Pyrite extraction by chromium II chloride and by elemental         analysis of the original rock, as described in documents         (Canfield et al., 1986; Acholla and Orr, 1993). According to         this approach, a hot hydrochloric acid (HCl) attack is first         carried out in order to extract all of the volatile sulfur         contained in rock samples. Once this step has been completed,         the samples are heat treated with a solution consisting of         hydrochloric acid (HCl) and chromium II chloride (CrCl₂)         allowing the pyrite (FeS₂) to be extracted. The sulfur effluent         (H₂S) released by the reduction of the pyrite by this solution         passes through a trap consisting of a silver nitrate solution         (AgNO₃), where it precipitates in form of silver sulfide (Ag₂S).         The Ag₂S precipitate obtained is weighed, which allows         stoichiometric quantification of the pyritic sulfur content,         assuming that the pyrite has been entirely converted to silver         sulfide. The organic sulfur content is then deduced by         difference between the total sulfur content, obtained by         elemental analysis of the original rock, and the pyritic sulfur         content. This method is based on the assumption that all of the         pyrite is reduced to H₂S.

This second laboratory method according to the prior art involves the following drawbacks:

it requires preparation and chemical separation steps that are extensive and dangerous since they use strong acids;

it does not enable measurement automation;

it is based on the assumption that all of the pyrite is reduced to H₂S. If part of the pyrite is not reduced, the pyritic sulfur content is underestimated and the organic sulfur content is overestimated. In particular, this may be the case for pyrite-rich samples.

-   -   Sulfur X-ray Absorption Near Edge Structure (S-XANES), as         described in documents (Vairavumuthy et al., 1997; Bolin, 2010):         according to this approach, the S-XANES technique provides         information about the oxidation state of the sulfur compounds.         In a typical analysis, the spectrum of a sample is deconvoluted         with various linear combinations of spectra of different sulfur         standards. The best adjustment is selected to indicate the red         composition of the various sulfur compounds of this sample. This         technique thus allows to quantitatively determine the pyritic         sulfur, the organic sulfur and the sulfates. In the case of rock         analysis, it is noted that very fine grinding of the sample is         often necessary so as to better quantify the pyritic sulfur,         whose peak is attenuated in the non finely ground samples.

This third laboratory method according to the prior art involves the following drawbacks:

it requires very fine grinding of the samples;

it requires access to a synchrotron, which is a very heavy and expensive equipment.

The present invention aims to overcome these drawbacks. Thus, the present invention relates to a method for characterizing the sulfur present in a rock sample, by distinctly quantifying the pyritic sulfur and the organic sulfur, in a fast, simple and precise manner.

SUMMARY OF THE INVENTION

The invention relates to a method for quantifying the pyritic sulfur in a sedimentary rock sample, wherein at least the following steps are carried out:

A. heating said sample in an inert atmosphere, between a first temperature ranging between 100° C. and 320° C. and a second temperature ranging between 600° C. and 700° C., by following a first temperature gradient ranging between 1° C./min and 30° C./min;

B. continuously oxidizing at least part of the effluents obtained from heating said sample in an inert atmosphere, continuously measuring a first amount of SO₂ released as a function of the time of said heating in an inert atmosphere, and determining at least a pyrolysis sulfur content S_(Pyrol) and a pyrolysis pyritic sulfur content S_(Pyrol) ^(Pyrit) from said first amount of SO₂;

C. heating in an oxidizing atmosphere the residue of said sample resulting from said heating in an inert atmosphere between a third temperature ranging between 280° C. and 320° C. and a fourth temperature greater than or equal to 800° C., by following a second temperature gradient ranging between 1° C./min and 30° C./min;

D. continuously measuring a second amount of SO₂ released as a function of the time of said heating in an oxidizing atmosphere, determining at least an oxidation sulfur content S_(Oxy) from said second amount of SO₂ and determining at least a total sulfur content S_(Total) by the sum of said pyrolysis sulfur content S_(Pyrol) and said oxidation sulfur content S_(Oxy).

According to the invention, at least a pyritic sulfur content S^(Pyrit) of said sample is determined from a formula of the type:

S ^(Pyrit) =p(α,β,γ)·S _(Pyrol) ^(Pyrit),

where p(α,β,γ) is a weighting function depending on a parameter α representing a proportion of said pyrolysis pyritic sulfur relative to said total sulfur, a parameter β representing an effect of the mineral matrix on said proportion, a parameter γ representing an effect of the organic matrix on said proportion, the values of said parameters being predetermined.

According to an implementation of the invention, said weighting function p(α,β,γ) can be written in the form:

${p\left( {\alpha,\beta,\gamma} \right)} = \frac{\left( {1 + \beta + \gamma} \right)}{\alpha}$

According to an embodiment of the invention, said sample is of reservoir rock type and said first temperature can range between 100° C. and 200° C.

According to another embodiment of the invention, said sample is of mother rock type and said first temperature can range between 280° C. and 320° C.

According to an implementation of the invention, parameter α can range between 0.40 and 0.46, and its value preferably is 0.43.

According to a variant embodiment of the invention, said rock sample is of clay type, and parameter β can range between 0.04 and 0.7, and its value preferably is 0.38.

According to another variant of the invention, said rock sample is of marl type, and parameter β can range between 0.7 and 0.9, and its value preferably is 0.78.

According to an alternative variant of the invention, said rock sample is of limestone type, and parameter β can range between 0.85 and 0.97, and its value preferably is 0.9.

According to an embodiment of the invention, said rock sample contains an organic matter of lacustrine and/or marine origin, and the value of parameter γ is 0.

According to another embodiment of the invention, said rock sample contains an organic matter of terrestrial origin, and parameter γ can range between 0.23 and 0.29, and its value preferably is 0.26.

According to a variant embodiment of the invention, said fourth temperature ranges between 800° C. and 900° C., and an organic sulfur content S^(Org) can be determined according to the formula:

S _(Org) =S _(Total) −S ^(Pyrit).

According to another variant of the invention, said fourth temperature is greater than 1150° C. and preferably less than 1250° C., and a sulfate sulfur content S_(Oxy) ^(Suifa) can be additionally determined from said second amount of SO₂, and an organic sulfur content can be deduced therefrom with the formula:

S ^(Org) =S _(Total) −S ^(Pyrit) −S _(Oxy) ^(Sulfa).

According to an implementation of the invention, said pyrolysis sulfur content and/or said pyrolysis pyritic sulfur content can be determined from said first amount of SO₂ and from a pyrolysis sulfur calibration coefficient established on a reference sample whose sulfur content is known, said reference sample being preferably native sulfur.

According to an implementation of the invention, said oxidation sulfur content can be determined from said second amount of SO₂ and from an oxidation sulfur calibration coefficient established on a reference sample whose sulfur content is known, said reference sample being preferably coal.

Advantageously, it is further possible to measure:

the amounts of hydrocarbon products, of CO and CO₂ contained in said effluents resulting from said heating of said sample in an inert atmosphere, and

the amounts of CO and CO₂ contained in the effluents resulting from said heating of the effluents resulting from said heating in an oxidizing atmosphere.

BRIEF DESCRIPTION OF THE FIGURES

Other features and advantages of the method according to the invention will be clear from reading the description hereafter of embodiments given by way of non limitative example, with reference to the accompanying figures wherein:

FIG. 1a shows an example of a measurement performed with a SO₂ detector during a heating sequence in an inert atmosphere to which a rock sample is subjected,

FIG. 1b shows an example of a measurement performed with a SO₂ detector during a heating sequence in an oxidizing atmosphere to which a rock sample is subjected,

FIG. 2 shows curves representative of the amount of SO₂ released by four pure igneous pyrite samples of distinct masses during a heating sequence in an inert atmosphere,

FIG. 3a shows a histogram representative of the effect of the mineral matrix as a function of the mineral mixture class considered,

FIG. 3b shows a histogram representative of the average effect of clays, carbonates and intermediate formations on the proportion of sulfur in the pyrite released during pyrolysis as a function of the mineral mixture class considered.

FIG. 3c shows the evolution of the effect of the mineral matrix as a function of the mineral carbon,

FIG. 4a shows an estimation of the effect of the organic matrix on the amount of sulfur released by the pyrite during the pyrolysis phase as a function of a first series of pyrite-organic matter mixture classes,

FIG. 4b shows an estimation of the effect of the organic matrix on the amount of sulfur released by the pyrite during the pyrolysis phase as a function of a second series of pyrite-organic matter mixture classes,

FIGS. 5a, 5b and 5c respectively show the evolution of the total sulfur, pyritic sulfur and organic sulfur content for various rock samples obtained with the method according to the invention as a function of the total sulfur content obtained for these samples with a method according to the prior art.

DETAILED DESCRIPTION OF THE INVENTION

In general terms, one object of the invention is a method for distinctly quantifying the pyritic sulfur and the organic sulfur present in a rock sample.

The present invention may apply to any type of sedimentary rocks such as, for example, a mother rock, a reservoir rock or an unconventional mother rock. In particular, the present invention is suited for rock samples from marine mother rocks.

In general, the rock sample may have been taken for example by coring within an underground formation of interest or it may result from drill cuttings. Advantageously, the sample as taken is prepared (by washing, screening, sorting, etc.) so as to remove impurities (drilling mud for example, pollutants, etc.), then it is hand ground or mechanically crushed.

The method according to the invention is based on the measurement of the sulfur dioxide (SO₂) released by a rock sample first subjected to pyrolysis (i.e. heating in an inert atmosphere), then to oxidation (i.e. heating in an oxidizing atmosphere).

The method according to the invention can be advantageously, but not limitatively, implemented using the ROCK-EVAL® device (IFP Energies nouvelles, France), as described in patent EP-2,342,557 (U.S. Pat. No. 8,796,035).

The method according to the invention comprises at least the following steps:

-   -   1. Heating sequence in an inert atmosphere (pyrolysis)     -   2. Heating sequence in an oxidizing atmosphere (oxidation)     -   3. Pyritic sulfur quantification.

1. Heating Sequence in an Inert Atmosphere (Pyrolysis)

In this step, the sample considered is heated in an inert atmosphere (such as, for example, in a stream of nitrogen, helium) according to a predetermined time-varying temperature programme.

According to an implementation of the invention, this step is carried out using a pyrolysis oven, the sample of interest placed in the oven being swept by a non-oxidizing gas stream.

According to the invention, the sample is heated by pyrolysis between a temperature T1 ranging between 100° C. and 320° C., and a temperature T2 ranging between 600° C. and 700° C., preferably 650° C., the temperature rise following a temperature gradient (or heating rate) ranging between 1° C./min and 30° C./min, preferably between 20° C./min and 30° C./min, and it is more preferably 25° C./min. According to an implementation of the invention where the analysed sample is a reservoir rock, temperature T1 ranges between 100° C. and 200° C., and it is preferably 180° C. According to an implementation of the invention where the analysed sample is a mother rock, temperature T1 ranges between 280° C. and 320° C., and it is preferably 300° C.

According to the invention, at least part of the pyrolysis effluents is oxidized as they are released. The sulfur gases present in the pyrolysis effluents are thus oxidized to SO₂. According to an implementation of the invention, this oxidation of the pyrolysis effluents is performed using a combustion chamber, such as an oxidation oven, in the presence of an oxygen-containing gas and optionally of a catalyst.

According to the invention, the SO₂ thus generated is continuously measured as the pyrolysis progresses, using a SO₂ detector such as an ultraviolet (UV) or infrared (IR) spectrophotometer. A measurement of the SO₂ released during pyrolysis as a function of the pyrolysis time and/or temperature is thus obtained.

2. Healing Sequence in an Oxidizing Atmosphere (Oxidation)

In this second step, the solid sample residue obtained after the pyrolysis sequence as described in step 1 above is subjected to oxidation according to a predetermined time-varying temperature programme.

According to the invention, the sample is heated in an oxidizing atmosphere between a temperature T3 ranging between 280° C. and 320° C., preferably 300° C., and a temperature T4 greater than or equal to 800° C., the temperature rise following a temperature gradient (or heating rate) ranging between 1° C./min and 30° C./min, preferably between 20° C./min and 30° C./min, and it is more preferably 20° C./min.

According to an implementation of the invention, this step is carried out using an oxidation oven, the pyrolysis residue being swept by an air stream.

According to the invention, the SO₂ generated by the oxidation of the pyrolysis residue and contained in the oxidation effluents is continuously measured, i.e. during the heating sequence in an oxidizing atmosphere. The SO₂ measurement is for example performed using a UV or IR spectrophotometer. A measurement of the SO₂ released during oxidation, for example as a function of the oxidation time and/or temperature, is thus obtained.

3. Pyritic Sulfur Quantification

After carrying out the previous two steps, we have two curves representative of the SO₂ measurements performed in steps 1 and 2 described above.

FIG. 1a illustrates an example of a curve (C1) showing the measured amount of SO₂ (more precisely amplitude A measured by a SO₂ detector such as an ultraviolet spectrophotometer) as a function of the pyrolysis time (denoted by t), and it also shows the evolution of the pyrolysis temperature (denoted by T) as a function of the pyrolysis time. FIG. 1b illustrates an example of a curve (C2) showing the measured amount of SO₂ (more precisely amplitude A measured by a SO₂ detector such as an ultraviolet spectrophotometer) as a function of the oxidation time (denoted by t), and it also shows the evolution of the oxidation temperature (denoted by T) as a function of the oxidation time. For this example, and by way of illustration, temperature T1 was selected equal to 300° C., temperature T2 was selected equal to 650° C., temperature T3 was selected equal to 300° C. and temperature T4 was selected equal to 1200° C.

It is observed that each one of these curves comprises several peaks and is identifiable by the number of these peaks, their peak apex temperature, their shape and their area. Peak C corresponding to the release, during pyrolysis, of part of the sulfur contained in the pyrite (referred to as “pyrolysis pyritic sulfur” hereafter and denoted by S_(Pyrol) ^(Pyrit)) can notably be observed in curve C1. Peak F corresponding to the release of the sulfur contained in the sulfates (referred to as “sulfate sulfur” hereafter and denoted by S_(Oxy) ^(Sulfa)) during oxidation can be observed in curve C2. Furthermore, the first two peaks A and B of curve C1 correspond to the sulfur contained in the thermally labile organic compounds, which are vaporizable and thermally crackable respectively. Also, it is observed that curve C2 has two nearly-merging first peaks D and E respectively corresponding to organic sulfur contained in organic compounds, which are thermally refractory or were generated during the pyrolysis phase, and to pyritic sulfur. It can thus be noted that recording the SO₂ released during the oxidation step does not allow to distinguish between these two peaks and therefore between the organic sulfur and the pyritic sulfur.

In this step, according to the invention, the proportion of pyrolysis sulfur S_(Pyrol) released during pyrolysis, the proportion of oxidation sulfur S_(Oxy) released during oxidation of the pyrolysis residue and the proportion of pyrolysis pyritic sulfur S_(Pyrol) ^(Pyrit) released during pyrolysis are quantified from the measurements performed during the heating sequence in an inert atmosphere and the heating sequence in an oxidizing atmosphere.

According to an implementation of the invention, the proportion of pyrolysis sulfur S_(Pyrol) (respectively the proportion of oxidation sulfur S_(Oxy)) in the analyzed sample can be determined from the area under the measured SO₂ curve recorded during the pyrolysis heating sequence (respectively during the oxidizing heating sequence), divided by the mass of the analyzed sample, weighted by a pyrolysis sulfur calibration coefficient (respectively an oxidation sulfur calibration coefficient). These proportions are expressed in mass percent, i.e. in mass of pyrolysis sulfur (respectively of oxidation sulfur), divided by the mass of the sample and multiplied by 100.

According to an implementation of the invention, the proportion of pyrolysis pyritic sulfur S_(Pyrol) ^(Pyrit) can be determined from the area under the peak representative of the pyrolysis pyritic sulfur on the measured SO₂ curve recorded during the pyrolysis phase (see peak C in FIG. 1a ), divided by the mass of the analyzed sample and weighted by a pyrolysis sulfur calibration coefficient. The proportion of pyrolysis pyritic sulfur is expressed in mass percent, i.e. in mass of pyrolysis pyritic sulfur, divided by the mass of the sample and multiplied by 100.

According to an implementation of the invention, a pyrolysis sulfur calibration coefficient (respectively an oxidation sulfur calibration coefficient) can be determined from at least one reference sample whose sulfur content is known, the sample being subjected to a pyrolysis heating sequence (respectively an oxidizing heating sequence). Thereafter, the pyrolysis sulfur calibration coefficient is determined from the area under the measured curve of the SO₂ released by this reference sample during a pyrolysis heating sequence (respectively during an oxidizing heating sequence), itself divided by the mass of the reference sample. According to an implementation of the invention, the reference sample can be native sulfur for determining the pyrolysis sulfur calibration coefficient. According to an implementation of the invention, the reference sample can be coal for determining the oxidation sulfur calibration coefficient.

According to the invention, the total sulfur content S_(Total) is further determined as the sum of the two contents S_(Pyrol) and S_(Oxy), i.e.:

S _(Total) =S _(Pyrol) +S _(Oxy),

expressed in mass percent (wt. %), i.e. in mass of total sulfur divided by the mass of the sample and multiplied by 100.

According to the invention, the pyritic sulfur content S^(Pyrit) is determined with a formula of the type:

S ^(Pyrit) =p(α,β,γ)·S _(Pyrol) ^(Pyrit)

expressed in mass percent, i.e. in mass of pyritic sulfur divided by the mass of the sample and multiplied by 100, p(α,β,γ) being a weighting function depending on parameters α, β and γ, and these parameters have been previously determined, with:

parameter α, which represents the proportion of pyritic sulfur released during the pyrolysis phase in relation to the total sulfur thereof, and can be seen as a rate of thermal degradation of the pyrite. According to an implementation of the invention, parameter α ranges between 0.40 and 0.46, and its value preferably is 0.43:

parameter β, which represents the impact of the mineral matrix on the proportion of pyritic sulfur released during the pyrolysis phase. Indeed, the mineral matrix reduces the amount of sulfur of the pyrite released during the pyrolysis phase. According to an aspect of the invention, parameter β can range between 0.04 and 0.97, depending on the type of rock the sample studied has been taken from. According to an implementation of the invention where the rock sample studied is of clay type, parameter β can range between 0.04 and 0.7, and its value preferably is 0.38. According to an implementation of the invention where the rock sample studied is of marl type, parameter β can range between 0.7 and 0.9, and its value preferably is 0.78. According to an implementation of the invention where the rock sample studied is of limestone type, parameter β can range between 0.85 and 0.97, and its value preferably is 0.90;

parameter γ, which represents the impact of the organic matrix on the proportion of pyritic sulfur released during the pyrolysis phase. According to an implementation of the invention, parameter γ can range between 0 and 0.29, depending on the type of organic matter. According to an implementation of the invention where the organic matter present in the rock sample studied is of marine or lacustrine type, the value of parameter γ is 0 (no significant effect on the degradation of the pyrite during the pyrolysis phase). According to an implementation of the invention where the organic matter present in the rock sample studied is of terrestrial type, parameter γ can range between 0.23 and 0.29, and its value preferably is 0.26.

According to an implementation of the invention, weighting function p(α,β,γ) can be written in the form as follows:

${p\left( {\alpha,\beta,\gamma} \right)} = {\frac{\left( {1 + \beta + \gamma} \right)}{\alpha}.}$

4. Organic Sulfur Quantification

In this step, which is optional, the proportion of organic sulfur S^(Org) contained in the rock sample considered can be determined from at least the difference between the total sulfur content S_(Total) and the pyritic sulfur content S^(Pyrit).

According to a first variant of the invention where the end oxidation temperature T4 ranges between 800° C. and 900° C., the proportion of organic sulfur S_(Org) contained in said sample can be determined with a formula of the type:

S ^(Org) =S _(Total) −S ^(Pyrit)

According to a second variant of the invention where end oxidation temperature T4 ranges between 1150° C. and 1250° C., preferably 1200° C., the proportion of organic sulfur S^(Org) contained in the sample can be determined as follows:

quantifying a proportion of sulfate sulfurs S_(Oxy) ^(Sulfa) from the area under the peak representative of the sulfate sulfur of the measured SO₂ curve recorded during the oxidation step, divided by the mass of the analyzed sample and weighted by an oxidation sulfur calibration coefficient (see step 3 above for determination of this calibration coefficient);

determining the proportion of organic sulfur S^(Org) with a formula of the type:

S ^(Org) =S _(Total) −S ^(Pyrit) −S _(Oxy) ^(Sulfa).

Indeed, for this variant embodiment, we can distinguish peak S_(Oxy) ^(Sulfa) (see peak F in FIG. 1a ) which corresponds to the release, during oxidation, of the sulfur contained in the sulfates, occurring at high temperatures. Determination of the organic sulfur content is more precise according to this second embodiment of the invention.

5. Calibration of Parameters α, β and γ

According to an embodiment of the invention, parameters α and/or β and/or γ as defined above can be calibrated prior to implementing the method according to the invention, or while implementing the method according to the invention, for example prior to stage 1, stage 2 or stage 3 described above.

Calibration of Parameter α

According to an implementation of the invention, parameter α can be calibrated by estimating the proportion of pyritic sulfur released during the pyrolysis phase in relation to the total sulfur from at least one pure igneous pyrite sample. According to an implementation of the invention, a so-called pure pyrite can be obtained by cleaning a natural pyrite of these impurities by chemical attacks.

An example of calibration of parameter α is described hereafter. Four samples from a single pure igneous pyrite sample (respectively denoted by E1, E2 E3, E4) of different masses (respectively 2 mg, 3 mg, 4 mg and 8 mg) are each subjected to pyrolysis by means of the ROCK-EVAL® device (IFP Energies nouvelles, France). Notably for this example of calibration of parameter α, each sample was placed in the pyrolysis oven of the ROCK-EVAL® device and heating of the sample was carried out between 300° C. and 650° C., with a temperature ramp of 25° C./min and in a 150 ml/min nitrogen stream. Thereafter, the sulfur effluents released by each pure igneous pyrite sample considered were carried by the nitrogen stream into the combustion chamber (oxidation oven) of the ROCK-EVAL® device, where they were converted to SO₂ in a continuous stream, then the SO₂ was carried to a SO₂ detector where it was continuously quantified by means of the SO₂ detector of the ROCK-EVAL® device. The solid residue of each igneous pyrite sample obtained after the pyrolysis sequence was then placed in the oxidation oven of the ROCK-EVAL® device and heating of the sample was carried out between 300° C. and 850° C., with a temperature ramp of 20° C./min and in a 100 ml/min air stream. The released SO₂ effluents were carried to a SO₂ detector where they were continuously quantified by means of the SO₂ detector of the ROCK-EVAL® device.

FIG. 2 shows the recording over time t of the amount of SO₂ (more precisely the amplitude) released by samples E1, E2, E3 and E4 during the pyrolysis phase as described above. Curve T also shown in this FIG. 2 corresponds to the evolution of the temperature to which each sample considered is subjected during this pyrolysis phase. This figure notably shows the presence of peaks representative of the thermal degradation of the pyrite at the different masses analysed during the pyrolysis phase. The pyrolysis sulfur content of the igneous pyrite sample (proportion of pyrolysis pyritic sulfur) was calculated by multiplying by the sulfur content of the reference sample the area under each curve E1, E2, E3 and E4, divided by the mass of the sample, and related to the area under the measured curve of the SO₂ released by a reference sample (such as native sulfur) during the pyrolysis heating sequence, itself divided by the mass of the reference sample. The ratio between this pyrolysis pyritic sulfur content and the total sulfur content of the pyrite (described in step 3 above) is calculated. The results show that, whatever the mass analysed, the mass proportion of the pyritic sulfur that is released during pyrolysis is 0.43±0.03 wt %. The remaining proportion of pyritic sulfur at the end of the pyrolysis sequence (0.57±0.03 wt %) is subsequently released during the oxidation step (step 2 described above).

Thus, the calibration as described above allows to determine that parameter α ranges between 0.40 and 0.46, and its value is 0.43 on average.

Calibration of Parameter β

According to an implementation of the invention, we calibrate parameter β, which represents the impact of the mineral matrix on the amount of sulfur of the pyrite released during the pyrolysis phase from at least a mixture of pyrite and of at least one mineral type, this mixture being representative of the rock sample to be studied by the method according to the invention.

An example of calibration of parameter β for various mineral types is described below. For this example of calibration of parameter β, we made mixtures from the following two major mineral groups:

-   -   clay/silicate minerals, such as:         -   silica (Fontainebleau sand, France), the mixture made with             silica is the reference mixture because silica is known to             be non-reactive;         -   kaolinite (reference: CMS Kga 1b);         -   smectite (reference: Mx80);         -   illite (Velay clay, France): this sample naturally             containing carbonates, it was decarbonated with hydrochloric             acid;             -   carbonate minerals, such as:         -   calcite (France);         -   dolomite (Euguy, Spain);         -   siderite (Peru).

The following mixtures are then made:

-   -   2 mg pyrite+98 mg of each clay/silicate mineral;     -   2 mg pyrite+58 mg of each carbonate mineral;     -   2 mg pyrite+98 mg clays (all the day/silicate minerals in equal         parts ¼; ¼; ¼; ¼);     -   2 mg pyrite+58 mg carbonates (all the carbonate minerals in         equal ports ⅓; ⅓; ⅓);     -   2 mg pyrite+58 mg clays and carbonates with different         proportions. i.e.:         -   93% clays and 7% carbonates;         -   69% clays and 31% carbonates;         -   51% clays and 49% carbonates;         -   26% clays and 74% carbonates.

These various samples are then subjected to steps 1 and 2 as described above using the ROCK-EVAL® device (IFP Energies nouvelles, France). More precisely, each sample is placed in the pyrolysis oven of the ROCK-EVAL® device, then heating of the sample is carried out between 300° C. and 650° C., with a temperature ramp of 25° C./min and in a 150 ml/min nitrogen stream. According to an implementation of the invention, the sulfur effluents released by each sample are carried by a nitrogen stream to the combustion chamber (oxidation oven) of the ROCK-EVAL® device, where they are converted to SO₂ in a continuous stream, then the SO₂ is carried to the SO₂ detector of the ROCK-EVAL® device where it s continuously quantified. The solid residue of each sample obtained after the pyrolysis sequence is then placed in the oxidation oven of the ROCK-EVAL® device and heating of the sample is carried out between 300° C. and 850° C., with a temperature ramp of 20° C./min and in a 100 ml/min air stream. The released SO₂ effluents are carried to a SO₂ detector where they are continuously quantified by means of the SO₂ detector of the ROCK-EVAL® device.

What is referred to as “mineral matrix effect” hereafter is the quantity expressed with a formula of the type:

${E_{Min} = {\frac{S_{Pyrol}^{{Pyrit},{ref}} - S_{Pyrol}^{{Pyrit},{Matrix}}}{S_{Pyrol}^{{Pyrit},{ref}}}*100}},$

where S_(Pyrol) ^(Pyrit,ref) is the pyrolysis pyritic sulfur released by a reference sample (consisting of pure igneous pyrite and silica) and S_(pyrol) ^(Pyrit,Matrix) is the pyrolysis pyrtic sulfur released by a considered mixture (pure igneous pyrite plus a mineral or a mineral mixture). To evaluate this quantity, the proportion of pyrolysis pyritic sulfur is determined as described in step 3 above, for a reference sample and for a considered mixture S_(Pyrol) ^(Pyrit,Matrix).

FIG. 3a shows a histogram representative of the effect E_(Min) of the mineral matrix as a function of the class of mixtures considered in the case of clay/silicate and carbonate minerals, more precisely for the following mixture classes:

-   -   M1: mixtures consisting of pyrite and quartz (reference sample);     -   M2: mixtures consisting of pyrite and kaolinite;     -   M3: mixtures consisting of pyrite and illite;     -   M4: mixtures consisting of pyrite and smectite;     -   M5: mixtures consisting of pyrite and calcite;     -   M6: mixtures consisting of pyrite and dolomite;     -   M7: mixtures consisting of pyrite and siderite.

FIG. 3b shows a histogram representative of the average effect E_(Min) of the clays, the carbonates and the intermediate formations on the proportion of sulfur in the pyrite released during pyrolysis for the following mixtures:

-   -   M8: mixtures consisting of 100% clays;     -   M9: mixtures consisting of 93% clays and 7% carbonates;     -   M10: mixtures consisting of 69% clays and 31% carbonates;     -   M11: mixtures consisting of 51% clays and 49% carbonates;     -   M12: mixtures consisting of 26% days and 74% carbonates;     -   M13: mixtures consisting of 100% carbonates.

FIGS. 3a and 3b also show the error bars for each histogram bar. These error bars were obtained by estimating a standard deviation established from repeated analyses as described above.

Thus, the results obtained by implementing the method for calibrating parameter β as described above for the various mixtures described highlight that the mineral matrix can reduce the proportion of sulfur in the pyrite released during the pyrolysis phase. However, this effect is very variable depending on the type of mineral present. The relative reduction of the proportion of sulfur released by the pyrite during pyrolysis ranges between 0% and 40% in the presence of clay/silicate minerals and between 60% and 98% in the presence of carbonate minerals (see FIG. 3a ). The average effect of the clays is 6%, whereas that of the carbonates reaches 93% (see FIG. 3b ). An increasing evolution of the effect E_(Min) of the matrix as a function of the proportion of clays and of carbonates in the mixture is observed between these two extremes (see FIG. 3b ).

FIG. 3c shows the evolution of effect E_(Min) of the mineral matrix as a function of the mineral carbon (denoted by MinC hereafter), a parameter that can be measured for example with the ROCK-EVAL® device (IFP Energies nouvelles, France), and which is an indicator of the carbonate content of the mixtures. It can be observed in this figure that the MinC varies in a range between 0 wt % and 12 wt % which corresponds to a calcite equivalent between 0 wt % and 100 wt %. This parameter enables to define three types of lithology: clays, marls and limestones. Area (A) in FIG. 3c represents the area of clays with calcite equivalent carbonate contents ranging between 0 wt % and 30 wt % (0≤MinC clays<3.6 wt %). In this clay formation area, the effect of the matrix on the amount of sulfur of the pyrite released during the pyrolysis phase ranges between 6% and 70%, with an average of 38%. Area (B) in FIG. 3c represents the zone of marls, which have calcite equivalent carbonate contents ranging between 30% and 70% (3.6≤MinC marls<8.4 wt %). In this marl formation area, the average value of the matrix effect on the amount of sulfur of the pyrite released during the pyrolysis phase ranges between 70% and 87%, with an average of 78%. Area (C) in FIG. 3c represents the area of limestones with calcite equivalent carbonate contents ranging between 70 wt % and 100 wt % (8.4≤MinC limestones≤12 wt %). In this limestone formation area, the average value of the matrix effect on the amount of sulfur of the pyrite released during the pyrolysis phase ranges between 87% and 94%, with an average of 90%.

Thus, parameter β ranges between 0.06 and 0.94 depending on the type of sedimentary formation, and more precisely, in the case of:

-   -   Clays: the value of parameter β is 0.38 on average;     -   Marls: the value of parameter β is 0.78 on average;     -   Limestones: the value of parameter β is 0.90 on average.

Calibration of Parameter γ

According to an implementation of the invention, we calibrate parameter γ, which represents the impact of the organic matrix on the amount of sulfur released by the pyrite during the pyrolysis phase from at least a mixture consisting of pyrite and of organic matter representative of that present in the rock sample to be studied. In natural rock samples, notably in mother rocks and in reservoir rocks, the pyrite is found in the presence of organic matter.

An example of calibration of parameter γ is described hereafter.

According to an implementation of the invention comprising a step of calibrating parameter γ for various types of organic matter, we make mixtures consisting of pyrite and different types of organic matter conventionally denoted by:

-   -   type I: lacustrine organic matter, such as the Green River         shales (Eocene, USA);     -   type II: marine organic matter, such as the paper shales of the         Paris Basin (Toarcian, France);     -   type IIS: organic sulfur-rich marine organic matter, such as the         Phosphoria Formation (Permian, USA);     -   type III: terrestrial organic matter, such as the Calvert Bluff         Formation (Paleocene, USA).

According to an implementation of the invention, mixtures such as the following can be made:

-   -   mixture of type A: 2 mg pyrite+2 mg organic matter;     -   mixture of type B: 2 mg pyrite+4 mg organic matter.

These mixtures are representative of a typical composition of the kerogens of sedimentary formations.

What is referred to as “organic matrix effect” hereafter is the quantity expressed with the formula as follows:

$E_{Org} = {\frac{S_{Pyrol}^{{Pyrit} + {{MO}\mspace{14mu} {obtenu}}} - S_{Pyrol}^{{Pyrit} + {{MO}\mspace{14mu} {attendu}}}}{S_{Pyrol}^{{Pyrit} + {{MO}\mspace{14mu} {attendu}}}} \times 100}$

where S_(Pyrol) ^(Pyrit+MO obtsnu) is the pyrolysis pyritic sulfur obtained after analysis of the mixture consisting of pyrite and organic matter (as described in step 3) and S_(Pyrol) ^(Pyrit+MO attendu) is the expected pyrolysis pyritic sulfur value of the mixture. This theoretical reference value is calculated as follows:

analysing each organic matter sample alone, using the ROCK-EVAL® device (IFP Energies nouvelles, France), so as to quantify its pyrolysis pyritic sulfur content (as described in step 3);

analysing the pyrite alone, using the ROCK-EVAL® device (IFP Energies nouvelles, France), so as to quantify its pyrolysis pyritic sulfur content (as described in step 3);

proportionally adding, as a function of the pyrite/organic matter ratio, the pyrolysis pyritic sulfur of the pyrite and the pyrolysis pyritic sulfur of the organic matter.

FIG. 4a shows the effect E_(Org) of the organic matrix on the amount of sulfur released by the pyrite during the pyrolysis phase for the mixtures of type A, with:

-   -   MA1: mixture consisting of 100% pyrite;     -   MA2: mixture consisting of 50% pyrite and 50% organic matter of         type I;     -   MA3: mixture consisting of 50% pyrite and 50% organic matter of         type II;     -   MA4: mixture consisting of 50% pyrite and 50% organic matter of         type IIS;     -   MA5: mixture consisting of 50% pyrite and 50% organic matter of         type III.

FIG. 4b shows the effect E_(Org) of the organic matrix on the amount of sulfur released by the pyrite during the pyrolysis phase for the mixtures of type B, with:

-   -   MB1: mixture consisting of 100% pyrite;     -   MB2: mixture consisting of 30% pyrite and 70% organic matter of         type I;     -   MB3: mixture consisting of 30% pyrite and 70% organic matter of         type II;     -   MB4: mixture consisting of 30% pyrite and 70% organic matter of         type IIS;     -   MB5: mixture consisting of 30% pyrite and 70% organic matter of         type III.

The results obtained by implementing the method of calibrating parameter γ as described above for the various mixtures described above show that there is nearly no organic matter effect concerning types I, II and IIS. Indeed, the organic matter effect is below 6% for this mixture type (see FIGS. 4a and 4b ). However, the organic matter of type III seems to have a significant effect on the amount of sulfur of the pyrite released during the pyrolysis phase (see FIGS. 4a and 4b ). Indeed, the effect of the organic matter of type III is 17% on average in mixture MA5 and 26% in mixture MB5, a mixture whose proportion between pyrite and organic matter is the most representative of that of kerogens in the majority of the sedimentary formations (see FIGS. 4a and 4b ).

Thus, parameter γ ranges between 0 and 0.29 depending on the type of organic matter present, and more precisely, in the case of an organic matter:

-   -   of type I, II or IIS, the value of γ is 0 (FIGS. 4a and 4b );     -   of type III, γ ranges between 0.23 and 0.29, and its value is         0.26 on average (FIG. 4b ).

According to an implementation of the invention, steps 1 and 2 described above can be implemented by means of the ROCK-EVAL® device (IFP Energies nouvelles, France) developed by the applicant and described notably in patent EP-2,342,557 (U.S. Pat. No. 8,796,035). Indeed the ROCK-EVAL® device comprises at least:

-   -   a pyrolysis oven in a non-oxidizing atmosphere,     -   means for oxidizing the pyrolysis sulfur effluents,     -   means for continuous measurement of the amount of SO₂ contained         in said effluents after oxidation,     -   means for transferring the pyrolysis residues to an oxidation         oven,     -   an oxidation oven in an oxidizing atmosphere,     -   means for continuous measurement of the amount of SO₂ contained         in said part after oxidation.

Furthermore, this device can also comprise means for measuring the hydrocarbon compounds released during pyrolysis, as well as a means of detecting carbon monoxide (CO) and carbon dioxide (CO₂).

The method can also be implemented using a single pyrolysis oven that can operate in a non-oxidizing atmosphere and in an oxidizing atmosphere, cooperating with a device for detecting and measuring the amount of sulfur dioxide (SO₂).

Application Examples

The method according to the invention is applied, in a first application example, to a series of thirteen samples from a rock known as Grey Shale Member, located in the Toarcian of the Whitby Mudstone Formation of the Cleveland Basin, UK. The Grey Shale Member is on interval of marine shales deposited in an oxygen-containing environment, intercalated by three sulfur-rich sedimentary layers referred to as sulfur bands. These three layers sedimented in an anoxic (oxygen-free) to euxinic (deeper, oxygen-free and beneath a sulfide-rich water layer) environment.

The method according to the invention is also applied, in a second application example, to a sample from a rock known as Black Band, which is also a shale interval of the Toarcian of the Whitby Mudstone Formation.

The method according to the invention is applied, in a third application example, to a series of eight samples from a rock known as Kimmeridge Clay Formation of the Wessex-Channel Basin in Dorset, UK. The interval studied, of the Kimmeridgian-Tithonian age, consists of an alternation of clays, marls and limestones.

The pyritic sulfur and the organic sulfur present in these samples are determined according to the method described above, by means of the ROCK-EVAL® device (IFP Energies nouvelles, France). More precisely, each sample is placed in the pyrolysis oven of the ROCK-EVAL® device, then heating of the sample is performed between 300° C. and 650° C., with a temperature ramp of 25° C./min and in a 150 ml/min nitrogen stream. According to an implementation of the invention, the sulfur effluents released by each sample are carried by a nitrogen stream into a combustion chamber (also referred to as oxidation oven) of the ROCK-EVAL® device, where they are converted to SO₂ in a continuous stream, then the SO₂ is carried to the SO₂ detector of the ROCK-EVAL® device where they are continuously quantified. After pyrolysis, each sample residue is transferred from the pyrolysis oven to the oxidation oven of the ROCK-EVAL® device and heating of the sample is carried out between 300° C. and 850° C. or 1200° C. depending on the implementation, with a temperature romp of 20° C./min and in a 100 ml/min air stream. The SO₂ effluents released by this oxidation are carried to the SO₂ detector of the ROCK-EVAL® device where they are continuously quantified. The pyritic sulfur content and the organic sulfur content of each rock sample analysed are deduced by implementing the method according to the invention. Thereafter, they are compared with those obtained with the kerogen elemental analysis method described above (by ICP-AES for iron and by infrared for sulfur), referred to as method according to the prior art hereafter.

FIGS. 5a, 5b and 5c respectively show the evolution of the proportion of total sulfur, pyritic sulfur and organic sulfur in each sample of the first application example EX1 (i.e. the 13 Grey Shale Member samples), for the sample of the second application example EX2 (i.e. the Black Band sample) and for each sample of the third application sample EX3 (i.e. the 8 Kimmeridge Clay Formation samples) obtained with the method according to the invention INV, as a function of the total sulfur content obtained for the same samples with the method according to the prior art AA.

FIG. 5a shows a very strong correlation between the total sulfur contents determined with the method according to the invention and with the method according to the prior art (correlation with a slope close to 1), confirming the validity of the total sulfur content determination for a sample with the method according to the invention.

Similarly, FIG. 5b shows a very strong correlation between the pyritic sulfur contents determined with the method according to the invention and with the method according to the prior art (correlation with a slope close to 1), confirming the validity of the pyritic sulfur content determination with the method according to the invention.

FIG. 5c shows a not so good correlation line concerning the organic sulfur content determined with the method according to the invention and with the method according to the prior art. Now, in the method according to the invention, the organic sulfur content is entirely deduced from the total and pyritic sulfur contents determined with the method of the invention (see step 3 above), whose values are valid (see the discussion relative to FIGS. 5a and 5b above). This lack of correlation can be due to the fact that the majority of the samples selected have a low organic sulfur content. Indeed, the organic sulfur content of the samples selected predominantly ranges between 0 wt % and 1 wt % (prior art values) or between 0 wt % and 3 wt % (values obtained with the method according to the invention) (FIG. 5c ). Thus, it is possible that the organic sulfur contents obtained here are of the order of magnitude of the measurement error of each method. Indeed, repetition of the analyses performed using the method according to the invention for various samples shows that the standard deviation on the measurement is on average 0.1 wt % for the total sulfur and 0.2 wt % for the pyritic and organic sulfur. Besides, repetition of the analyses performed using the method according to the prior art shows that the standard deviation on the measurement is on average 0.1 wt % for the total sulfur, 0.5 wt % for the pyritic sulfur and 0.6 wt % for the organic sulfur. It is therefore noted that the method according to the prior art seems to be less precise than the method according to the invention. This may be explained by the fact that the prior art combines two different techniques (ICP-AES and infrared) and therefore two possible error sources, and by the fact that this prior art is based on the assumption that all of the iron contained in the organic matter is pyritic. Now, if the iron contained in the organic matter also comes in other forms, such as oxides or other sulfides than pyrite, the pyritic sulfur content is overestimated and the organic sulfur content is underestimated. On the other hand, the method according to the invention uses only one type of measurement (measurement of the SO₂ released by a sample) and it is based on a perfect distinction between the pyritic sulfur and the organic sulfur during the pyrolysis phase. Thus, the method according to the invention is less uncertain than the prior art.

Furthermore, the method of the invention is faster since the implementation of the method according to the invention for the 13 Grey Shale Member samples, an application example described above, was conducted in about 15 hours for the 13 samples, whereas the implementation of the method according to the prior art with the same application example was conducted in about 7 days. 

1-17: (canceled)
 18. A method for quantifying pyritic sulfur in a sedimentary rock sample, comprising: A. heating the sample in an inert atmosphere, between a first temperature ranging between 100° C. and 320° C. and a second temperature ranging between 600° C. and 700° C., to produce effluents by following a first temperature gradient ranging between 1° C./min and 30° C./min; B. continuously oxidizing at least part of the effluents obtained from heating the sample in an inert atmosphere and continuously measuring a first amount of SO₂ released as a function of the time of the heating in an inert atmosphere, and determining at least a pyrolysis sulfur content and a pyrolysis pyritic sulfur content from the first amount of SO₂; C. heating in an oxidizing atmosphere a residue of the sample resulting from the heating in the inert atmosphere between a third temperature ranging between 280° C. and 320° C. and a fourth temperature at least equal to 800° C., by following a second temperature gradient ranging between 1° C./min and 30° C./min; D. continuously measuring a second amount of SO₂ released as a function of time of the heating in the oxidizing atmosphere and determining at least an oxidation sulfur content from the second amount of SO₂ and determining at least a total sulfur content by a sum of the pyrolysis sulfur content and the oxidation sulfur content, and wherein at least the pyritic sulfur content of the sample is determined from a formula: S ^(Pyrit) =p(α,β,γ)·S _(Pyrol) ^(Pyrit), where p(α,β,γ) is a weighting function depending on a parameter α representing a proportion of the pyrolysis pyritic sulfur relative to the total sulfur, a parameter β representing an effect of a mineral matrix on the proportion, a parameter γ representing an effect of organic matrix on the proportion with values of the parameters being predetermined.
 19. A method as claimed in claim 18, wherein the weighting function p(α,β,γ) is written as: ${p\left( {\alpha,\beta,\gamma} \right)} = \frac{\left( {1 + \beta + \gamma} \right)}{\alpha}$
 20. A method as claimed in claim 18, wherein the sample is reservoir rock and the first temperature ranges between 100° C. and 200° C.
 21. A method as claimed in claim 18, wherein the sample is mother rock and the first temperature ranges between 280° C. and 320° C.
 22. A method as claimed in claim 18, wherein parameter α ranges between 0.40 and 0.46.
 23. A method as claimed in claim 22 wherein α is 0.43.
 24. A method as claimed in claim 18, wherein the rock sample is clay and parameter β ranges between 0.04 and 0.7.
 25. A method as claimed in claim 24 wherein β is 0.38.
 26. A method as claimed in claim 18, wherein the rock sample is marl and parameter β ranges between 0.7 and 0.9.
 27. A method as claimed in claim 26 wherein β is 0.78.
 28. A method as claimed in claim 18, wherein the rock sample is limestone and parameter β ranges between 0.85 and 0.97.
 29. A method as claimed in claim 28 wherein β is 0.9.
 30. A method as claimed in claim 18, wherein the rock sample contains an organic matter of at least one of lacustrine and marine origin, and a value of parameter γ is
 0. 31. A method as claimed in claim 18, wherein the rock sample contains an organic matter of terrestrial origin and parameter γ ranges between 0.23 and 0.29.
 32. A method as claimed in claim 31 wherein γ is 0.26.
 33. A method as claimed in claim 18, wherein the fourth temperature ranges between 800° C. and 900° C., and an organic sulfur content S^(Org) is determined according to a formula as follows: S ^(Org) =S _(Total) −S ^(Pyrit).
 34. A method as claimed in claim 18, wherein the fourth temperature is greater than 1150° C. and less than 1250° C., and a sulfate sulfur content S_(Oxy) ^(Sulfa) is additionally determined from the second amount of SO₂, and organic sulfur content is determined with a formula: S^(Org)=S_(Total)−S^(Pyrit)−S_(Oxy) ^(Sulfa), wherein. S^(Pyrit) is pyritic sulfur content and S_(Total) is a total amount of sulfur that is present.
 35. A method as claimed in claim 18, wherein at least one of the pyrolysis sulfur content and the pyrolysis pyritic sulfur content is determined from the first amount of SO₂ and from a pyrolysis sulfur calibration coefficient established on a reference sample whose sulfur content is known.
 36. A method as claimed in claim 35, wherein the reference sample is native sulfur.
 37. A method as claimed in claim 18, wherein the oxidation sulfur content is determined from the second amount of SO₂ and from an oxidation sulfur calibration coefficient established from a reference sample whose sulfur content is known.
 38. A method as claimed in claim 37, wherein the reference sample is coal.
 39. A method as claimed in claim 18, comprising: measuring amounts of hydrocarbon products of CO and CO₂ contained in the effluents that result from the heating of the sample in an inert atmosphere; and measuring amounts of CO and CO₂ contained in the effluents resulting from the heating in an oxidizing atmosphere. 